Process of painting with inks with colored resin emulsion particles

ABSTRACT

An aqueous ink jet ink composition comprised of water, colorant, and colored resin emulsion particles generated from olefinic monomers, wherein at least one of said olefinic monomers contains a colorant, wherein the olefinic colorant component is prepared from the condensation reaction of a functional colorant with an olefinic containing reactive material, and which reaction generates                    
     wherein Dye represents a colorant chromophore, and R is a carbonyl, carboxylate, oxygen, or arylene, and R′ is hydrogen or alkyl.

This application is a divisional of application Ser. No. 08/903,700,filed Jul. 31, 1997 now U.S. Pat. No. 6,251,987.

BACKGROUND OF THE INVENTION

The use of resin emulsion particles in pigmented inks is illustrated incopending application U.S. Ser. No. 08/869,962, the disclosure of whichis wholly incorporated herein by reference, which discloses, forexample, a resin emulsion comprised of from about 40 to 60 weightpercent of benzyl methacrylate, from about 5 to about 20 weight percentof methacrylic acid, and from about 20 to about 40 percent by weight ofpolyethyleneglycol methacrylate, or more generally, a low molecularweight polyethylene glycol capped with a methacrylate or acrylate group.

The present invention is generally directed to ink compositions. Morespecifically, the present invention is directed to aqueous inkcompositions particularly suitable for use in ink jet printingprocesses, and especially thermal ink jet processes, wherein the inksenable images with excellent smear resistant characteristics, and whichinks contain unsaturated dye molecules incorporated into the resinemulsion particle by emulsion polymerization. Moreover, with the inks ofthe present invention the optical density of the developed images isexcellent, paper curl is minimized and image smearing is minimal, oravoided. In embodiments, the present invention relates to imagingprocesses with ink jet inks comprised of water, colorant, especiallydye, or pigment, and resin emulsion particles. Further, images developedwith the inks of the present invention in embodiments enable ink jetprints of excellent resolution, acceptable and improved optical density,excellent waterfastness, minimum or very low showthrough, and excellentMFLEN.

PRIOR ART

Ink jet printing can be considered a non-impact method that generatesdroplets of ink that are deposited on a substrate, such as paper ortransparent film, in response to an electronic digital signal.

In existing thermal ink jet printing, the printhead typically comprisesone or more ink jet ejectors, such as disclosed in U.S. Pat. No.4,463,359, the disclosure of which is totally incorporated herein byreference, each ejector including a channel communicating with an inksupply chamber, or manifold, at one end and having an opening at theopposite end, referred to as a nozzle. A thermal energy generator,usually a resistor, is located in each of the channels, a predetermineddistance from the nozzles. The resistors are individually addressed witha current pulse to momentarily vaporize the ink and form a bubble whichexpels an ink droplet. As the bubble grows, the ink rapidly bulges fromthe nozzle and is momentarily contained by the surface tension of theink as a meniscus. This is a temporary phenomenon, and the ink isquickly propelled toward a print sheet. As the bubble begins tocollapse, the ink still in the channel between the nozzle and bubblestarts to move toward the collapsing bubble, causing a volumetriccontraction of the ink at the nozzle and resulting in the separationfrom the nozzle of the bulging ink as a droplet. The feed of additionalink provides the momentum and velocity for propelling the droplet towarda print sheet, such as a piece of paper. Since the droplet of ink isemitted only when the resistor is actuated, this type of thermal ink jetprinting is known as “drop-on-demand” printing. Other types of ink jetprinting, such as continuous-stream or acoustic, are also known.

In a single-color ink jet printing apparatus, the printhead typicallycomprises a linear array of ejectors, and the printhead is movedrelative to the surface of the print sheet, either by moving the printsheet relative to a stationary printhead, or vice-versa, or both. Insome types of apparatus, a relatively small printhead moves across aprint sheet numerous times in swathes, much like a typewriter.Alternatively, a printhead which consists of an array of ejectors andextends the full width of the print sheet may be passed once down theprint sheet to give full-page images, in what is known as a “full-widtharray” (FWA) printer. When the printhead and the print sheet are movedrelative to each other, imagewise digital data is used to selectivelyactivate the thermal energy generators in the printhead over time sothat the desired image will be created on the print sheet.

With the demand for higher resolution printers, the nozzles in ink jetprinters are decreasing in size. Nozzle openings are typically about 50to 80 micrometers in width or diameter for 300 spi printers. With theadvent of 600 spi printers, these nozzle openings are typically about 10to about 40 micrometers in width or diameter. These small dimensionsrequire inks that do not plug the small openings.

Another important measured property for an ink jet ink is high opticaldensity and the latency or decap time, which is the length of time overwhich an ink remains fluid in a printhead opening or nozzle when exposedto air and, therefore, capable of firing a drop of ink at its intendedtarget. Latency is the maximum idling times allowed for ink to be jettedby a printer with a speed equal to or greater than 5 m/s (equivalent toan ink traveling a distance of 0.5 millimeter in less than 100 μs)without a failure. This test is run with the printhead or nozzlesuncovered or decapped and generally at a relative humidity of 15percent. The time interval is the longest length of time that theprinthead, uncovered, will still fire a specified drop without dropdisplacement or loss of density. The longer the latency time rating, themore desirable the ink. The inks of the present invention possess manyof these characteristics in embodiments thereof.

Moreover, an important characteristic for ink jet inks, especially forpigment, such as carbon black, based inks, is for the pigment dispersionto remain stable throughout the life of the ink jet cartridge. Dye inkjet inks can suffer from deficiencies in waterfastness, smear resistanceand lightfastness after being printed on various substrates. Pigmentsprovide an image, on a wide variety of substrates, with in someinstances high optical density with high waterfastness, excellent smearresistance and acceptable lightfastness. Therefore, pigments are apreferred alternative to dyes provided the pigment dispersions can bestabilized to prevent flocculation and/or aggregation and settling. Somecosolvents that are suitable as clogging inhibitors causedestabilization of pigment dispersions and, therefore, cannot readily beused in pigmented inks.

There is thus a need for aqueous ink compositions that can be utilizedin high resolution ink jet printers. Additionally, there is a need forinks that provide high latency and also remain stable throughout thelife of the ink jet cartridge. There is also a need for inks withcolorants, such as dyes or pigments, that provide high optical densityin a single application or pass. More importantly, there is a need forink jet inks wherein paper curl, and/or image smearing can be eliminatedor minimized when such inks are selected for ink jet printing processes.

SUMMARY OF THE INVENTION

The present invention relates to aqueous ink jet ink compositionscomprising water, colorant, especially pigment particles, and certaincolored resin emulsion particles. More specifically, the presentinvention relates to inks containing a resin emulsion derived fromolefinic monomers, and wherein one of the olefinic monomers contains acolorant, especially a dye. In embodiments, the olefinic dye moleculescan be prepared from the condensation reaction of a functional colorant,especially a dye with an olefinic containing reactive material such asmetacryloyl chloride, acryloyl chloride or 4-isocyanate-styrene asillustrated by the formula

that is wherein an unsaturated isopropenyl group is chemically bonded,or linked to the R group, and wherein Dye represents the colorant,especially dye chromophore, and R is a carbonyl, oxygen, arylene with,for example, from 7 to about 25 carbon atoms, such as phenylene, and thelike, and R′ is a hydrogen or alkyl group of from about 1 to about 6carbon atoms. Thereafter, the colored resin emulsion is prepared bymixing the olefinic dye monomer in water, optionally with other olefinicmonomers, or monomer, with or without chain transfer agents,surfactants, like Triton X-100, ammonium persulfate, and sodiumdodecylbenzene sulfonate, and heating, for example, to about 70 to about80° C. (Centigrade), or other suitable temperature, for a suitableduration, for example from, for example, about 3 to about 9 hours.Subsequently, the ink is prepared by mixing the resin emulsion generatedwith pigment, or a pigment dispersion, ink additives such as sulfolane,and the like, and more specifically, wherein a black resin emulsion ismixed with carbon black pigment, especially Levanyl carbon blackobtained from Bayer, and wherein the carbon black is a dispersion,especially a one percent dispersion, with sulfolane, glycol,trimethylolpropane, pyrrolidone, and the like.

More specifically, there is provided an aqueous ink jet ink compositioncomprised of water, colorant, and colored resin emulsion particlesgenerated from olefinic monomers, wherein at least one of said olefinicmonomers contains a colorant, wherein the olefinic colorant component isprepared from the condensation reaction of a functional colorant with anolefinic containing reactive material, and which reaction generates

wherein Dye represents a colorant chromophore, and R is a carbonyl,carboxylate, oxygen, or arylene, and R′ is hydrogen or alkyl; an inkwherein the colorant is a dye of black, cyan, yellow, magenta, red,blue, green, orange or brown; an ink wherein the colorant is a dyechemically bound to a polymer resin emulsion generated by the emulsionpolymerization of an olefinic dye monomer with at least one unsaturatedmonomer; an ink wherein the unsaturated monomer is methyl acrylate,methyl methacrylate, ethyl acrylate, ethyl methacrylate, propylacrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, hexylacrylate, hexyl methacrylate, pentyl acrylate, pentyl methacrylate,heptyl acrylate, heptyl methacrylate, octyl acrylate, octylmethacrylate, nonyl acrylate, nonyl methacrylate, decylacrylate,decylmethacrylate, lauryl acrylate, lauryl methacrylate, stearylacrylate, stearyl methacrylate, dodecyl acrylate, or dodecylmethacrylate, polyethylene glycol methacrylate, and which monomer isselected in an effective amount of from about 20 to about 90 weightpercent of the resin emulsion, and preferably of from about 20 to about60 weight percent of the resin emulsion; an ink wherein the unsaturatedmonomer is methacrylic acid, benzyl methacrylate, or polyethyleneglycol(meth)acrylate; an ink wherein the olefinic dye monomer is representedby the formula

Y—R—CHR′=CH₂

wherein Y is NCO, Cl, or Br; R is CO or an aromatic group of phenylene,and R′ is H or CH₃; an ink wherein the olefinic dye molecule is obtainedfrom the condensation of a functional dye and a reactive unsaturatedcomponent; an ink wherein the functional dye is of the formulas

A—(Y—OH)_(p)  (I)

where A is an organic chromophore, Y is a straight chain or branchedpolyoxyalkylene substituent with from about 1 to about 200 carbons, andp is from about 1 to 4 and represents the number of chains perchromophore bonded to the polyoxyalkylene substituent by a linking groupof N, NR₃, O, S, SO₂, SO₂N, SO₂NR₃, CO₂, CON, CONR₃, where R is H, C₁ toC₁₂ alkyl, phenyl or benzyl; or

A—(Y—X—C(O)—R₁—C(O)OH)_(p)  (I)

where A is an organic chromophore, Y is a polyalkylene substituent withfrom about 1 to about 100 carbon atoms, p is an integer of from about 1to 4; X is a nucleophile of O, NR₂, or S wherein R₂ is H or a C₁ to C₁₈alkyl; R₁ is alkylene, alkenylene, phenylene, and phenylenealkylene, anyof which may be optionally substituted with alkyl, alkenyl or arylgroups, provided that the total number of carbon atoms is from about 2to 30; an ink wherein the reactive unsaturated component is acryloxychloride, acryloxy bromide, acryloxy iodide, methacryloxy chloride,methacryloxy bromide, 4-isocyanato-1-isopropenylbenzene, orisocyanato-isopropenyl; an ink wherein the resin emulsion possesses anM_(w) of from about 5,000 grams per mole to about 300,000 grams permole; an ink wherein the resin emulsion possesses an M_(n) of from about2,000 grams per mole to about 150,000 grams per mole; an ink furthercontaining ink additives; an ink wherein the ink additive is asurfactant; an ink wherein the surfactant is selected in an amount offrom about 0.005 to about 20 weight percent; an ink wherein thesurfactant is selected in an amount of from about 0.1 to about 10 weightpercent; an ink wherein the colorant is present in an amount of fromabout 4 to about 10 percent by weight of said ink composition; an inkwherein the colorant is a pigment of carbon black, cyan, magenta,yellow, or mixtures thereof; an ink with a latency of from about 20 toabout 60 seconds; a smear ratio value of from about 0 to about 0.06, andan optical density for the images developed with said ink of from about1.2 to about 1.6; an ink further containing biocides and humectants; anink wherein the biocides and humectants are each present in an amount offrom about 0.01 to about 50 weight percent; an imaging process whichcomprises the development of an image with the invention ink compositionillustrated herein, and which image is fixed on a substrate; a highresolution printing process comprising applying in imagewise fashion toa substrate in a printer having at least one nozzle of a channel widthor diameter ranging from about 10 to about 40 microns the inventionaqueous ink jet ink; and a process wherein the substrate is paper andpaper curl is minimized or eliminated, or wherein the substrate ispaper, image smearing is minimized or eliminated, and the opticaldensity of the developed images is at least 1.25; an ink wherein arylenecontains from 7 to about 25 carbon atoms.

In embodiments, the olefinic dye monomer can be prepared by the reactionof a polyol-dye chromophore with 4-isocyanato-styrene as illustrated bythe formula;

wherein attached to the two (2) position of the aromatic ring isisopropenyl.

More specifically, the olefinic dye monomer can be prepared by charginga reactor with about 411 grams of a polyol-dye, such as REACTINT BLACKX57AB™ obtained from Milliken Chemicals, and about 60 grams of4-isocyanato-1-isopropenylbenzene and about 1 gram of UNICURE® as thecondensation catalyst, and which catalyst is available from, and wasobtained from Uniroyal Corporation. The resulting mixture was stirred at70° C. for a duration of about 3 hours, followed by cooling to roomtemperature to provide the olefinic dye monomer product.

The colored resin emulsion can be prepared by emulsion polymerization ofthe aforementioned olefinic dye monomer by conventional process. Morespecifically, the colored resin emulsion can be prepared by charging avessel with about 50 grams of the aforementioned olefinic dye monomerobtained from REACTINT BLACK X57AB™ and 4-isocyanato-isopropenylbenzene,about 45 grams of butyl methacrylate, about 10 grams of methacrylicacid, about 400 grams of water, about 2.0 grams of sodium dodecylbenzenesulfonate, about 3 grams of potassium persulfate, and about 2 grams ofTriton X-100 obtained from Aldrich Chemicals. The mixture was thenstirred and heated to about 80° C. for a duration of about 6 hours.

The ink is formulated by the mixing of from about 0.5 to about 5 eightpercent of the formed resin emulsion with from about 3 to about 7 eightpercent of pigment, such as carbon black dispersion obtained from BayerCorporation as Levanyl carbon black, from about 10 to about 60 percentby weight of cosolvent such as 2-pyrrolidinone, sulfolane,trimethylopropane, glycol or mixtures thereof, the remaining about 10 toabout 40 weight percent of the ink being water. Other additives such asbiocides, or jetting additives may also be added to the ink. Resinemulsions are illustrated in the copending application mentionedhereinbefore.

Also, the present invention relates to a high resolution printingprocess comprising applying the invention ink composition in imagewisefashion to a substrate. The ink possesses a latency of, for example, atleast about 20 seconds and, for example, from about 20 to about 75seconds in, for example, a printer with at least one nozzle of a channelwidth or diameter of from about 10 to about 40 microns and whereinsubstrate, such as paper curl, is minimized or eliminated.

Important embodiments of the present invention include an imagingprocess which comprises the development of an image with the aqueous inkjet ink composition illustrated herein; an imaging process whichcomprises the development of an image with the invention aqueous ink jetink composition, and wherein images with minimal curling and minimalsmearing are obtained; a high resolution printing process comprisingapplying in imagewise fashion to a substrate in a printer having atleast one nozzle of a channel width or diameter ranging from about 10 toabout 4 microns the invention aqueous ink jet ink composition; a processfor reducing or eliminating paper curl and improving optical density ina xerographic ink jet apparatus which comprises generating images in theapparatus and developing the images with the invention aqueous ink jetink composition.

Imaging processes of the present invention in embodiments thereofpossess numerous advantages including excellent waterfastness,acceptable lightfastness, low product cost, high image resolution,excellent print quality on a variety of substrates, excellent jettingcapability with high drop velocity, longer latency, larger drop mass ordrop volume which provides optimal optical density in a single pass,high frequency response which allows for high speed printing, excellentprinthead recoverability and maintainability, excellent ink stability,minimal ink and pigment settling, a lack of printhead kogation and moreimportantly, wherein the inks when selected for ink jet processes enablethe minimization of paper curl, smearing is avoided or minimized, andthe image optical densities are excellent. The inks possess excellentwaterfastness between, for example, from about 95 to about 100 percent,and acceptable lightfastness between, for example, from about 90 toabout 100 percent. More preferably, the inks possess a smear ratiodefined as optical density adjacent to the image after smearing dividedby the original optical density of the image in the range of betweenfrom about 0 to about 0.10. The image optical density that is preferredis in the range of 1.25 to about 1.5.

The olefinic dye molecule is generally prepared from the condensation ofa dye chromophore containing at least one functional group such as anhydroxyl moiety, with an olefinic reactive compound such as anisocyanate or acryloxy chloride. In embodiments, the dye is in the formof a chromophore having at least one —OH group. The presence of the —OHgroup permits the dye to be chemically bonded to the olefinic materialby reaction with the isocyanate group or acid chloride group of theolefinic reactive compound. Examples of such dyes are those having thefollowing formula

A—(Y—OH)_(p)

where A is an organic dye chromophore, Y is a straight chain or branchedpolyoxyalkylene such as polyethylene glycol or polypropylene glycolwith, for example, from about 1 to about 200 carbon atoms, and prepresents the number of chains per chromophore and preferably is fromabout 1 to about 4 chains. The chromophore is generally covalentlybonded to the polyoxyalkylene substituent by a linking group such as N,NR₃, O, S, SO₂, SO₂N, SO₂NR₃, CO₂, CON, CONR₃, wherein R is H, C₁ to C₁₂alkyl, aryl with, for example, 6 to about 24 carbon atoms, such asphenyl or benzyl. These dyes may be represented generally by the formula

A—(Y—X—C(O)—R₁—C(O)OH)_(p)

where A is an organic chromophore, Y is a polyalkylene substituent with,for example, from about 1 to about 100 carbon atoms, p is an integer offrom about 1 to 4; X is a nucleophile of O, NR₂, and S wherein R₂ is Hor a C₁ to C₁₈ alkyl; R₁ is alkylene, alkenylene, phenylene, andphenylenealkylene, any of which may be optionally substituted withalkyl, alkenyl or aryl groups, provided that the total number of carbonatoms is from about 2 to about 30. The dyes are described in more detailin U.S. Pat. No. 5,310,887, the disclosure of which is totallyincorporated herein by reference.

The reactive olefinic material utilized for the condensation reactionwith the dye is represented by the formula

Y—R—CHR′=CH₂

wherein Y is NCO, Cl, Br, F, I; R is CO or an aromatic group with, forexample, from 6 to about 30 carbon atoms, such as phenylene, and R′ is Hor an alkyl such as a CH₃ group.

The reactive olefinic material or component selected for condensationwith the dye includes acryloxy halides, such as acryloxy chloride,acryloxy bromide, acryloxy iodide, methacryloxy chloride, methacryloxybromide, 4-isocyanato-1-isopropenylbenzene, isocyanato-isopropenyl,mixtures thereof, and like. The reactive olefinic material is selectedin various amounts, for example effective amounts of from about 45 toabout 55 mole percent of the olefinic dye product.

The dye chromophore selected for the condensation reaction with thereactive olefinic material can be of any suitable color, such as black,cyan, magenta, yellow, red, blue, green, brown, mixtures thereof, andthe like, and present in the condensation product in various amounts,such as an amount of, for example, from about 45 mole percent to about55 mole percent. Preferred dyes are cyan and magenta dyes available fromMilliken, such as REACTINT BLUE X17AB™, REACTINT X3LV™, PALMER BLUE™,REACTINT BLUE X19™, and magenta REACTINT RED X52™; REACTINT YELLOW X15™,REACTINT BLACK 57AB™, REACTINT BLACK X40LV™, REACTINT ORANGE X38™,REACTINT VIOLET X80™, mixtures thereof, and the like.

The olefinic monomer selected for the colored resin emulsion can, forexample, be alkyl acrylate or alkyl methacrylate, methyl acrylate,methyl methacrylate, ethyl acrylate, ethyl methacrylate, propylacrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, hexylacrylate, hexyl methacrylate, pentyl acrylate, pentyl methacrylate,heptyl acrylate, heptyl methacrylate, octyl acrylate, octylmethacrylate, nonyl acrylate, nonyl methacrylate, decylacrylate,decylmethacrylate, lauryl acrylate, lauryl methacrylate, stearylacrylate, stearyl methacrylate, dodecyl acrylate, or dodecylmethacrylate, polyethylene glycol methacrylate, and the like. Theolefinic monomer is utilized in an effective amount of, for example,from about 0 to about 60 weight percent of the resin emulsion, andpreferably of from about 10 to about 60 weight percent of the resinemulsion.

The liquid vehicles include water, or may comprise a mixture of waterand a miscible organic component, such as ethylene glycol, propyleneglycol, diethylene glycols, glycerine, dipropylene glycols, polyethyleneglycols, polypropylene glycols, amides, ethers, carboxylic acids,esters, alcohols, organosulfides, organosulfoxides, sulfones,dimethylsulfoxide, sulfolane, alcohol derivatives, carbitol, butylcarbitol, cellusolve, ether derivatives, amino alcohols, ketones, andother water miscible materials, and mixtures thereof.

When mixtures of water and water miscible organic liquids are selectedas the liquid vehicle, the water to organic ratio may be in anyeffective range, and typically is from about 100:0 to about 30:70,preferably from about 97:3 to about 50:50, although the ratio can beoutside these ranges. The non-water component of the liquid vehiclegenerally serves as a humectant which has a boiling point higher thanthat of water (100° C.). The pigment dispersion can be mixed withdifferent humectants or solvents in ink jet inks includingethyleneglycol, diethyleneglycol, propyleneglycol, dipropylene glycol,polyethylene glycols, polypropylene glycols, glycerine,trimethylolpropane, 1,5-pentanediols, 1,6-hexanediols, diols and triolscontaining 2 to 10 carbons; sulfoxides, for example dimethyl sulfoxides,alkylphenyl sulfoxides, and the like; sulfones, such as sulfolane,dialkyl sulfones, alkyl phenyl sulfones, and the like; amides such asN,N-dialkyl amides, N,N-alkyl phenyl amides, N-methylpyrrolidinone,N-cyclohexylpyrrolidinone, N,N-diethyltoluamide, and the like; etherssuch as alkyl ether derivatives of alcohol, etherdiols, and ethertriolsincluding butylcarbitol, alkyl polyethylene glycols, and the like; urea,betaine, or the thio (sulfur) derivatives of the aforementionedcomponents, such as, for example, thioethyleneglycol,trithioethyleneglycol, and the like. Desired penetrants, water solublepolymers, pH buffer, biocides, chelating agents (EDTA and the like), andoptional additives can also be included in the inks.

The liquid vehicle is generally present in an amount of from about 50 toabout 99.5 percent by weight, preferably about 55 to about 95 percent byweight, and more preferably from about 60 to about 90 percent by weight,although the amount may be outside these ranges.

The colorant for the ink compositions is preferably, for example, apigment, or a mixture of one or more pigments. The pigment can be black,cyan, magenta, yellow, red, blue, green, brown, mixtures thereof, andthe like, and is preferably the carbon black Levanyl carbon blackobtained from Bayer, carbon black products obtained from CabotCorporation. Examples of suitable black pigments include various carbonblacks such as channel black, furnace black, lamp black, and the like.Colored pigments include red, green, blue, brown, magenta, cyan, andyellow particles, and mixtures thereof. Illustrative examples of magentapigments include 2,9-dimethyl-substituted quinacridone andanthraquinone, identified in the Color Index as CI 60710, CI Solvent Red19, and the like. Illustrative examples of suitable cyan pigmentsinclude copper tetra-4-(octadecyl sulfonamido) phthalocyanine, X-copperphthalocyanine pigment, listed in the color index as CI 74160, CIPigment Blue, and Anthradanthrene Blue, identified in the Color Index asCI 69810, Special Blue X-2137, and the like. Illustrative examples ofyellow pigments that can be selected include diarylide yellow3,3-dichlorobenzidene acetoacetanilides, a monoazo pigment identified inthe Color Index as CI 12700, CI Solvent Yellow 16, a nitrophenyl aminesulfonamide identified in the Color Index as Foron Yellow SE/GLN, CIDispersed Yellow 33, 2,5-dimethoxy-4-sulfonanilidephenylazo-4′-chloro-2,5-dimethoxy acetoacetanilide, Permanent YellowFGL, and the like. The preferable pigment dispersions include carbonblacks, such as Hostafine Black (T and TS), Sunsperse 9303, and LevanylBlack A-SF. Of these, Levanyl Black A-SF is the most preferred.Colorants include dyes, pigments, mixtures thereof, mixtures ofpigments, mixtures of dyes, and the like.

Preferably, the pigment particle size is small to primarily enable astable colloidal suspension of the particles in the liquid vehicle andto prevent clogging of the ink channels when the ink is selected for athermal ink jet printer. Preferred particle average diameters aregenerally from about 0.001 to about 5 microns, and more preferably fromabout 0.01 to about 3 microns, although the particle size may be outsidethese ranges. A more preferred pigment particle size includes particleshaving at least 70 percent of the particles being below about 0.1 micronwith no particles being greater than about 1.0 micron (measured on aHodaka CAPA 700 Particle Size Analyzer). More preferably, the pigmentparticle size includes particles having at least 90 percent of theparticles being below 0.1 micron with no particles being greater than1.0 micron.

The colorant, especially pigment, is present in the ink composition invarious effective amounts and generally from about 1 to about 20 percentby weight, preferably from about 3 to about 10 percent by weight, morepreferably from about 4 to about 9 percent by weight, and mostpreferably from about 5 to about 8 percent, although the amount may beoutside of these ranges.

Polymeric additives can also be added to the inks to, for example,enhance the viscosity of the ink, including water soluble polymers, suchas gum arabic, polyacrylate salts, polymethacrylate salts, polyvinylalcohols, hydroxypropyl cellulose, hydroxyethyl cellulose,polyvinylpyrrolidinone, polyvinylether, polyethyleneimines derivatizedwith polyethylene oxide and polypropylene oxide, such as the DISCOLE®series available from DKS International, Tokyo, Japan, the JEFFAMINE®series available from Texaco, Bellaire, Tex., and the like. Polymericadditives may be present in the ink of the present invention in amountsof from 0 to about 10 percent by weight, preferably from about 0.001 toabout 8 percent by weight, and more preferably from about 0.01 to about5 percent by weight, although the amount may be outside these ranges.

Further, optional additives include biocides such as DOWICIL™ 150, 200,and 75, benzoate salts, sorbate salts, and the like, present in anamount of from 0 to about 10 percent by weight, preferably from about0.001 to about 8 percent by weight, and more preferably from about 0.01to about 4.0 percent by weight, although the amount may be outside theseranges; penetration control additives such as N-methylpyrrolidinone,sulfoxides, ketones, lactones, esters, alcohols, butyl carbitol, benzylalcohol, cyclohexylpyrrolidinone, 1,2-hexanediol, and the like, presentin an amount of from 0 to about 50 percent by weight, and preferablyfrom about 5 to about 40 percent by weight, although the amount may beoutside these ranges, pH controlling agents such as acids or bases,phosphate salts, carboxylates salts, sulfite salts, amine salts, and thelike, present in an amount of from 0 to about 1 percent by weight,preferably from about 0.001 to about 1 percent by weight, and morepreferably from about 0.01 to about 1 percent by weight, although theamount may be outside these ranges, or the like.

Other examples of suitable ink additives include those illustrated inU.S. Pat. No. 5,223,026 and U.S. Pat. No. 5,207,825, the disclosure ofeach of which is totally incorporated herein by reference.

Aqueous ink compositions, according to the present invention, may alsobe provided by mixing the formed inks with humectants, and other inkadditives. The mixing can be accomplished by various methods includinghomogenizing, sonification, microfluidization, mechanical mixing,magnetic stirring, high speed jetting, and the like.

The dispersed pigment can be used as is, but preferably the thoroughlymixed pigment dispersion mixture is first centrifuged by a batch processor a continuous process utilizing commercially available equipment, suchas bottle centrifuges, preparative ultracentrifuges, analyticalultracentrifuges, zonal centrifuges, tubular centrifuges, diskcentrifuges, continuous conveyor-discharge centrifuges, basketcentrifuges, liquid cyclones, and the like to remove large pigmentparticles from the ink. Centrifuging should be conducted for a timesufficient to remove large size particles and at a rate of from about4,000 to about 8,000 rpm. The continuous centrifuge process is veryuseful in the commercial production of large quantities of pigment inkfor the separation of large pigment particles from the ink. The ink isalso preferably subjected to a filtration process which utilizes variouscommercial filtration media including cartridges constructed from nylon,polyester, TEFLON®, polysulfone, glass fiber and polyethylene, and othersuitable polymeric materials; membranes; porous ceramic media; cloth;and the like. The filter should be of a size to remove particles greaterthan 3 μm in size, preferably greater than 1.2 μm in size, mostpreferably greater than 1 μm in size. Any suitable filtration method,such as continuous and/or batch filtration methods, may be used.Continuous filtration methods are preferred for large scale productionof pigment inks. Inks which have been centrifuged and filtered so as topreferably remove particles greater than 1 μm in size from the ink aresuitable for use as ink jet inks because of their ability to not clogthe ink jet and their long latency and jetting stability.

The ink may be applied to a suitable substrate in imagewise fashion.Application of the ink to the substrate can be by any suitable processcompatible with aqueous-based inks, such as flexographic printing, penplotters, continuous stream ink jet printing, drop-on-demand ink jetprinting (including both piezoelectric and thermal ink jet processes),or the like. The substrate employed can be any substrate compatible withaqueous-based inks, including plain paper, such as Xerox Corporationseries 10 paper, Xerox Corporation 4024 paper, or the like, coatedpapers, such as those available from Jujo, transparency materialssuitable for aqueous inks or ink jet printing processes, or the like.

The following Examples and Comparative Examples and data are provided.

EXAMPLE I

Preparation of an olefinic dye monomer from the condensation reaction of50 mole percent of 4-isocyanato-1-isopropenylbenzene and 50 mole percentof a dye chromophore available as REACTINT BLACK X57AB™ from MillikenChemicals.

To a 2 liter vessel were charged 411 grams of REACTINT BLACK X57AB™obtained from Milliken Chemicals, and 60 grams of4-isocyanato-1-isopropenylbenzene with about 1 gram of Unicure catalystavailable from Uniroyal Chemical Company, and which catalyst may be anaromatic aniline. The resulting mixture was stirred at 70° C. for aduration of 3 hours, followed by cooling to room temperature, about 25°C., to provide the olefinic dye monomer product.

EXAMPLE II

Preparation of an olefinic dye monomer from the condensation reaction of50 mole percent of 4-isocyanato-1 -isopropenylbenzene, and 50 molepercent of a dye chromophore available as REACTINT YELLOW X17™ fromMilliken Chemicals.

To a 2 liter vessel were charged 350 grams of REACTINT YELLOW X17™obtained from Milliken Chemicals, and 60 grams of4-isocyanato-1-isopropenylbenzene with about 1 gram of Unicure as thecondensation catalyst, and which catalyst was obtained from Uniroyal.The resulting mixture was stirred at 70° C. for a duration for 3 hours,followed by cooling to room temperature, about 25° C. throughout, toprovide the above olefinic dye monomer product.

EXAMPLE III

Preparation of an olefinic dye monomer from the condensation reaction of50 mole percent of 4-isocyanato-1-isopropenylbenzene, and 50 molepercent of a dye chromophore available as REACTINT BLUE X15™ fromMilliken Chemicals.

To a 2 liter vessel were charged 400 grams of REACTINT BLUE X15™obtained from Milliken Chemicals, and 60 grams of4-isocyanato-1-isopropenylbenzene with about 1 gram of Unicure as thecondensation catalyst, and which catalyst was obtained from Uniroyal.The resulting mixture was stirred at 70° C. for a duration of 3 hours,followed by cooling to room temperature to provide the olefinic dyemonomer product.

EXAMPLE IV (GS705)

Preparation of a colored resin emulsion derived from 30 weight percentof the olefinic dye monomer of Example I, 49 weight percent of benzylmethacrylate, and 21 weight percent of methacrylic acid.

To a 2 liter vessel were added 250 grams of water, 2.0 grams of TritonX-100 surfactant obtained from Aldrich Chemicals, and 1.8 grams ofsodium dodecylbenzene sulfonate. The resulting mixture was stirred forabout 1 hour, after which were added 47 grams of the olefinic dyemonomer product of Example I, 66.5 grams of benzyl methacrylate, 28.3grams of methacrylic acid, and 1.8 grams of ammonium persulfate. Themixture was then heated to 80° C. for a duration of 6 hours to result ina black colored emulsion resin.

EXAMPLE V (GS706)

Preparation of a colored resin emulsion derived from 34 weight percentof the olefinic dye monomer of Example I, 47 percent by weight of benzylmethacrylate, and 19 percent by weight of methacrylic acid.

To a 2 liter reaction vessel were added 250 grams of water, 2.0 grams ofTriton X-100 surfactant obtained from Aldrich Chemicals, and 1.8 gramsof sodium dodecylbenzene sulfonate. The resulting mixture was stirredfor about 1 hour, and thereafter, there were added 50 grams of theolefinic dye monomer product of Example I, 61 grams of benzylmethacrylate, 28.3 grams of methacrylic acid, and 1.8 grams of ammoniumpersulfate. The mixture was then heated to 80° C. for a duration of 6hours to result in a black colored emulsion resin.

EXAMPLE VI (GS707)

Preparation of a colored resin emulsion derived from 53 weight percentof the olefinic dye monomer of Example I, 29 weight percent of benzylmethacrylate, and 18 weight percent of methacrylic acid.

To a 2 liter reaction vessel were added 250 grams of water, 2.0 grams ofTriton X-100 surfactant obtained from Aldrich Chemicals, and 1.8 gramsof sodium dodecylbenzene sulfonate. The mixture was stirred for about 1hour, after which were added 74 grams of the olefinic dye monomerproduct of Example I, 41 grams of benzyl methacrylate, 25 grams ofmethacrylic acid and 1.8 grams of ammonium persulfate. The mixture wasthen heated to 80° C. for a duration of 6 hours to result in a blackcolored emulsion resin.

EXAMPLE VII (GS708)

Preparation of a colored resin emulsion derived from 53 weight percentof the olefinic dye monomer of Example II, 29 weight percent of benzylmethacrylate, and 18 weight percent of methacrylic acid.

To a 2 liter reaction vessel were added 250 grams of water, 2.0 grams ofTriton X-100 surfactant obtained from Aldrich Chemicals, and 1.8 gramsof sodium dodecylbenzene sulfonate. The resulting mixture was stirredfor about 1 hour, and thereafter, there were added 47 grams of theolefinic dye monomer product of Example II, 66.5 grams of benzylmethacrylate, 28.3 grams of methacrylic acid, and 1.8 grams of ammoniumpersulfate. The mixture was then heated to 80° C. for a duration of 6hours to result in a blue colored emulsion resin.

EXAMPLE VIII

Preparation of a colored resin emulsion derived from 53 weight percentof the olefinic dye monomer of Example III, 29 weight percent of benzylmethacrylate, and 18 weight percent of methacrylic acid.

To a 2 liter reaction vessel were added 250 grams of water, 2.0 grams ofTriton X-100 surfactant obtained from Aldrich Chemicals, and 1.8 gramsof sodium dodecylbenzene sulfonate. The resulting mixture was stirredfor about 1 hour, after which were added 47 grams of the olefinic dyemonomer product of Example III, 66.5 grams of benzyl methacrylate, 28.3grams of methacrylic acid, and 1.8 grams of ammonium persulfate. Themixture was then heated to 80° C. for a duration of 6 hours to result ina yellow colored emulsion resin.

The Levanyl carbon black dispersion (obtained from Bayer Corporation)was centrifuged to remove large (>1 μm) particles. The carbon blackdispersion was filtered through a 1 μm glass fiber filter prior tomaking inks. All Examples herein utilize the preprocessed Levanyl carbonblack dispersion, unless otherwise specified.

EXAMPLE IX Preparation of Ink

A black colored ink jet ink composition was prepared by mixing 16 weightpercent of diethylene glycol (obtained from Aldrich), 15 weight percentof 2-pyrrolidinone (obtained from Aldrich), and water (ink balance tototal 100 percent). The vehicle resulting and the colored resin emulsionof Example IV, about 0.55 percent solids equivalent, were added to thevehicle mixture and stirred for about 5 to 10 minutes. The resultantmixture was added to the Levanyl carbon black dispersion (obtained fromBayer Corporation), 7 weight percent of carbon black. The ink mixturewas stirred for about 5 minutes, and thereafter, the ink mixture wasfiltered through a 1 μm glass fiber filter. The final ink comprised 16weight percent of diethylene glycol, 15 weight percent of2-pyrrolidinone, 0.55 weight percent solids equivalent of the coloredresin emulsion, 7 weight percent of Levanyl carbon black, and 1 weightpercent of polymeric dispersant, naphthalene sulfonic acid formaldehydecondensate, which is contained in the commercially available Levanylcarbon black, and the balance is water to total 100 weight percent.

EXAMPLE IX Preparation of Ink:

A black colored ink jet ink composition was prepared by mixing 20 weightpercent of Sulfolane (obtained from Bayer) and water (ink balance tototal 100 percent). The colored resin emulsion of Example V, about 1percent solids equivalent, was added to the prepared vehicle mixture andstirred for about 5 to 10 minutes. The resultant mixture was added toLevanyl carbon black dispersion (obtained from Bayer Corporation), 7weight percent carbon black. The ink mixture was stirred for about 5minutes, and then the ink mixture was filtered through a 1 μm glassfiber filter. The final ink comprised 20 weight, 1 weight percent solidsequivalent of the colored resin emulsion, 7 weight percent of Levanylcarbon black, and 1 weight percent of the polymeric dispersant,naphthalene sulfonic acid formaldehyde condensate which was contained inthe commercially available Levanyl carbon black, and the balance waswater to enable total of about 100 weight percent.

EXAMPLE XI Preparation of Ink

A black colored ink jet ink composition was prepared by mixing 16 weightpercent of diethylene glycol (obtained from Aldrich), 15 weight percentof 2-pyrrolidinone (obtained from Aldrich), and water (ink balance tototal 100 percent). The vehicle resulting and the colored resin emulsionof Example VI about 0.55 percent solids equivalent, was added to thevehicle mixture and stirred for about 5 to 10 minutes. The resultantmixture was added to the Levanyl carbon black dispersion (obtained fromBayer Corporation), 7 weight percent of carbon black. The ink mixturewas stirred for about 5 minutes and then the ink mixture was filteredthrough a 1 μm glass fiber filter. The final ink comprised 16 weightpercent of diethylene glycol, 15 weight percent of 2-pyrrolidinone, 0.55weight percent solids equivalent of the colored resin emulsion, 7 weightpercent of Levanyl carbon black, and 1 weight percent of the polymericdispersant, naphthalene sulfonic acid formaldehyde condensate, which wascontained in the commercially available Levanyl carbon black, and thebalance was water to enable a total of about 100 weight percent for allthe ink components.

EXAMPLE XII Preparation of Ink

A black colored ink jet ink composition was prepared by mixing 16 weightpercent of diethylene glycol (obtained from Aldrich), 15 weight percentof 2-pyrrolidinone (obtained from Aldrich), and water (ink balance tototal 100 percent). The vehicle resulting and the colored resin emulsionof Example VII, about 0.55 percent solids equivalent, were added to thevehicle mixture and stirred for about 5 to 10 minutes. The resultantmixture was added to the Levanyl carbon black dispersion (obtained fromBayer Corporation), 7 weight percent of carbon black. The ink mixturewas stirred for about 5 minutes, and thereafter, the ink mixture wasfiltered through a 1 μm glass fiber filter. The final ink comprised 16weight percent of diethylene glycol, 15 weight percent of2-pyrrolidinone, 0.55 weight percent solids equivalent of the coloredresin emulsion, 7 weight percent of Levanyl carbon black, and 1 weightpercent (weight percent throughout) of the polymeric dispersant,naphthalene sulfonic acid formaldehyde condensate, which was containedin the commercially available Levanyl carbon black, and the balance waswater to enable for all ink components a total of 100 weight percent.

Comparative Example 1 Preparation of Ink

A black colored ink jet ink composition was prepared by mixing 16 weightpercent of diethylene glycol (obtained from Aldrich), 15 weight percentof 2-pyrrolidinone (obtained from Aldrich), and water (ink balance tototal 100 percent). The resultant mixture was added to the Levanylcarbon black dispersion (obtained from Bayer Corporation), 7 weightpercent of carbon black. The ink mixture was stirred for about 5minutes. The ink mixture was then filtered through a 1 μm glass fiberfilter.

The final ink comprised 16 weight percent of diethylene glycol, 15weight percent of 2-pyrrolidinone, 7 weight percent of Levanyl carbonblack, and 1 weight percent of the polymeric dispersant, naphthalenesulfonic acid formaldehyde condensate, which was contained in thecommercially available Levanyl carbon black, and the balance was waterto enable for all ink components a total of 100 weight percent.

EVALUATIONS

The properties of the ink compositions were evaluated in the followingmanner:

A) Physical Properties

The viscosity of the ink was measured at 25° C. using a Brookfield ModelDV-11 viscometer.

The surface tension of the ink was measured at 25° C. using a Krussmodel K10T plate tensiometer.

The pH was measured at 25° C. using a Corning model 345 pH meter.

B) Smear Resistance

The images were placed in an ink jet printer HP850C (Hewlett Packard).After an image was printed, the image was allowed to stand, or remain atroom temperature, about 25° C., for 24 hours prior to evaluation. Theoptical density of the solid area was measured prior to smear testingusing a densitometer (X-Rite 428). The images were printed on severalmedia such as Xerox Courtland 4024DP and Image Series LX paper. A cleansheet of the matching paper was placed on top of the solid area image.Using a rub tester (Manufactured by Testing Machines Inc.), a 4 poundweight was placed on top of the covered image. At a speed of 85 rubs perminute, the image was subjected to 50 rubs at 25° C. and 50 percent RH.The area adjacent to the solid area image was measured using thedensitometer.

C) Stability

50 Grams of ink were placed in a capped bottle and allowed to stand at atemperature of 60° C. for 24 hours. The ink physical properties weremeasured after heat treatment. For comparison, the shelf no emulsionstanding ink was also measured for physical properties after 24 hours.Changes greater than about 0.4 centipoise units for viscosity indicateinstability. Observation of the ink standing on the shelf at roomtemperature, about 25° C. throughout, for settling were also tested forextended periods of up to 1.5 years.

D) Optical Density

An image was printed by an ink jet printer HP855C on each of thefollowing papers: Xerox Courtland 4024DP and Images Series LX. Theoptical density of the printed image was measured by an X-Ritedensitometer.

TABLE 1 Physical Properties for Stability Measured at 25° C. 60° C./24hour Heat Treatment Surface Surface Viscosity Tension Viscosity TensionExample cPs D/cm pH cPs D/cm pH IX 3.3 52 4.8 3.3 53 4.8 X 3.5 56 5.143.6 55 5.14 XI 3.7 56 5 3.7 56 4.98 XII 3.4 57 5.99 3.5 57 5.78 Compara-3.5 56 6.42 3.5 57 6.03 tive

The Examples with colored resin emulsion indicate that the addition ofresin emulsion did not cause instability in the ink formulations.Instability would be evident as an increase in viscosity, over about 0.4centipoise. Settling or precipitation was not evident for the inventionink Examples.

TABLE 2 Smear Ratio = Smear Optical density od/Image od Xerox ImageXerox Image Series Example 4024DP Series LX 4024DP LX IX 1.30 1.40 0.100.08 X 1.20 1.30 0.07 0.09 XI 1.26 1.37 0.05 0.10 XII 1.26 1.22 0.090.10 Comparative 1 1.27 1.30 0.13 0.18

These Examples indicate some enhancement in optical density at only 0.55weight percent solids equivalent of the color resin emulsion in the inkformulation contrasted to the Comparative Example.

Improvements in the smear were also found in contrast to the ComparativeExample.

The interaction of the colored resin emulsion and pigment on paperresulted in more pigment agglomerations on the surface of the paper.This allowed for higher optical density since some of the pigment didnot penetrate into the paper fibers. With the colored resin emulsionacting as a binder, the smear resistance was improved. The agglomeratesof the pigment and colored resin allowed for fixing onto the paper andamong particles. This imparts smear resistance.

Other modifications of the present invention may occur to those ofordinary skill in the art subsequent to a review of the presentapplication, and these modifications, including equivalents thereof, areintended to be included within the scope of the present invention.

What is claimed is:
 1. An imaging process which comprises thedevelopment of an image with an ink composition comprised of water,colorant, and colored resin emulsion particles generated from olefinicmonomers, wherein at least one of said olefinic monomers contains acolorant, wherein the olefinic colorant component is prepared from thecondensation reaction of a functional colorant with an olefiniccontaining reactive material, and which reaction generates

wherein Dye represents a colorant chromophore, and R is a carbonyl,carboxylate, oxygen, or arylene, and R′ is hydrogen or alkyl, and whichimage is optionally fixed on a substrate.
 2. A high resolution printingprocess comprising applying in imagewise fashion to a substrate in aprinter having at least one nozzle of a channel width or diameterranging from about 10 to about 40 microns an aqueous ink jet inkcomposition comprised of water, colorant, and colored resin emulsionparticles generated from olefinic monomers, wherein at least one of saidolefinic monomers contains a colorant, wherein the olefinic colorantcomponent is prepared from the condensation reaction of a functionalcolorant with an olefinic containing reactive material, and whichreaction generates

wherein Dye represents a colorant chromophore, and R is a carbonyl,carboxylate, oxyqen, or arylene, and R′ is hydrogen or alkyl, and whichimage is fixed on a substrate.
 3. A process in accordance with claim 1wherein the substrate is paper and paper curl is minimized oreliminated, or wherein the substrate is paper, image smearing isminimized or eliminated, and the optical density of the developed imagesis at least 1.25.
 4. A process in accordance with claim 2 wherein thecolorant is black, cyan, yellow, magenta, red, blue, green, orange,brown, or mixtures thereof.
 5. A process in accordance with claim 2wherein the colorant is a dye chemically bound to a polymer resinemulsion generated by the emulsion polymerization of an olefinic dyemonomer with at least one unsaturated monomer.
 6. A process inaccordance with claim 5 wherein said unsaturated monomer is methylacrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate,propyl acrylate, propyl methacrylate, butyl acrylate, butylmethacrylate, hexyl acrylate, hexyl methacrylate, pentyl acrylate,pentyl methacrylate, heptyl acrylate, heptyl methacrylate, octylacrylate, octyl methacrylate, nonyl acrylate, nonyl methacrylate,decylacrylate, decylmethacrylate, lauryl acrylate, lauryl methacrylate,stearyl acrylate, stearyl methacrylate, dodecyl acrylate, or dodecylmethacrylate, polyethylene glycol methacrylate, and which monomer isselected in an effective amount of from about 20 to about 90 weightpercent of the resin emulsion, and preferably of from about 20 to about60 weight percent of the resin emulsion.
 7. A process in accordance withclaim 6 wherein the unsaturated monomer is methacrylic acid, benzylmethacrylate, or polyethyleneglycol (meth)acrylate.
 8. A process inaccordance with claim 6 wherein the olefinic dye monomer is representedby the formula Y—R—CHR′=CH₂ wherein Y is NCO, Cl, or Br; R is CO or anaromatic group of phenylene, and R′ is H or CH₃.
 9. A process inaccordance with claim 8 wherein the olefinic dye molecule is obtainedfrom the condensation of a functional dye and a reactive unsaturatedcomponent.
 10. A process in accordance with claim 9 wherein thefunctional dye is of the formulas A—(Y—OH)_(p)  (I) where A is anorganic chromophore, Y is a straight chain or branched polyoxyalkylenesubstituent with from about 1 to about 200 carbons, and p is from about1 to 4 and represents the number of chains per chromophore bonded to thepolyoxyalkylene substituent by a linking group of N, NR₃, O, S, SO₂,SO₂N, SO₂NR₃, CO₂, CON, CONR₃, where R is H, C₁ to C₁₂ alkyl, phenyl orbenzyl; or A—(Y—X—C(O)—R₁—C(O)OH)_(p)  (II) where A is an organicchromophore, Y is a polyalkylene substituent with from about 1 to about100 carbon atoms, p is an integer of from about 1 to 4; X is anucleophile of O, NR₂, or S wherein R₂ is H or a C₁ to C₁₈ alkyl; R₁ isalkylene, alkenylene, phenylene, and phenylenealkylene, any of which maybe optionally substituted with alkyl, alkenyl or aryl groups, providedthat the total number of carbon atoms is from about 2 to
 30. 11. Aprocess in accordance with claim 9 wherein the reactive unsaturatedcomponent is acryloxy chloride, acryloxy bromide, acryloxy iodide,methacryloxy chloride, methacryloxy bromide,4-isocyanato-1-isopropenylbenzene, or isocyanato-isopropenyl.
 12. Aprocess in accordance with claim 2 wherein said resin emulsion possessesan M_(w) of from about 5,000 grams per mole to about 300,000 grams permole.
 13. A process in accordance with claim 2 wherein said resinemulsion possesses an M_(n) of from about 2,000 grams per mole to about150,000 grams per mole.
 14. A process in accordance with claim 2 furthercontaining ink additives.
 15. A process in accordance with claim 2wherein said colorant is present in an amount of from about 4 to about10 percent by weight of said ink composition.
 16. A process inaccordance with claim 2 wherein said colorant is a pigment of carbonblack, cyan, magenta, yellow, or mixtures thereof.
 17. A process inaccordance with claim 2 with an ink latency of from about 20 to about 60seconds; a smear ratio value of from about 0 to about 0.06, and anoptical density for the images developed with said ink of from about 1.2to about 1.6.
 18. A process in accordance with claim 2 wherein said inkfurther contains biocides and humectants.
 19. A process in accordancewith claim 18 wherein the biocides and humectants are each present in anamount of from about 0.01 to about 50 weight percent.